See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/330371749

High performance electrically conductive epoxy/reduced graphene oxide

adhesives for electronics packaging applications

Article  in  Journal of Materials Science Materials in Electronics · January 2019

DOI: 10.1007/s10854-019-00722-5

CITATIONS READS

0 84

3 authors, including:

Ruchi Aradhana
Central Institute of Plastics Engineering and Technology
5 PUBLICATIONS   15 CITATIONS   

SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Epoxy based electrically conductive adhesives View project

All content following this page was uploaded by Ruchi Aradhana on 29 January 2019.

The user has requested enhancement of the downloaded file.

Journal of Materials Science: Materials in Electronics
https://doi.org/10.1007/s10854-019-00722-5

High performance electrically conductive epoxy/reduced graphene

oxide adhesives for electronics packaging applications
Ruchi Aradhana1 · Smita Mohanty1,2 · Sanjay Kumar Nayak1,2

Received: 22 July 2018 / Accepted: 9 January 2019

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Abstract
In the present study, an attempt has been done to prepare an electrically conductive epoxy adhesive filled with the high
content of reduced graphene oxide (rGO) (i.e. 10–50 wt%). The lap shear test was performed to study the adhesive strength
of epoxy-based adhesive systems. The test results revealed that adhesive with 40 wt% rGO possessed highest shear strength
which is 72.8% higher over unmodified epoxy. While the tensile test results showed a decrement of 33% in tensile strength
even with the introduction of 10 wt% rGO. The unnotched and notched impact strength of epoxy resin found to be increas-
ing up to 51% and 100% respectively, when 30 wt% rGO was incorporated within the matrix. The fractography analysis of
notched impact samples was examined by scanning electron microscopy and unveils that crack pinning is the toughening
mechanism for E–rGO adhesive systems. The dispersion assessment of rGO within the epoxy matrix was visualized by
transmission electron microscopy technique, revealing the effective distribution of rGO in epoxy matrix. The volume and
surface conductivity was increased up to 3.44 × 10−08 S/m and 8.54 × 10−06 S with 50 wt% rGO addition, which are five and
five-fold higher in comparison to the epoxy resin. At 35 °C, the thermal conductivity was enhanced by ~ 408% as compared
to pristine epoxy, when 50 wt% rGO was included. Fourier transform infra‑red spectroscopy spectra was used to study the
nature of interaction between rGO and epoxy matrix. The adhesive systems showed higher thermo-stability with the intro-
duction of rGO as detected by thermo-gravimetric analysis technique.

1 Introduction properties of polymers [5]. Among the preparation methods

Graphene, a monolayer of two-dimensional sheet consists
of ­sp2-bonded carbon atoms arranged in an atomically thick
honeycomb structure, has seized the attention of research-
ers in both scientific community and industries [1, 2]. As a
thinnest [2] and strongest [1] material, it possesses many
outstanding properties such as excellent strength (130 GPa),
high modulus (1000 GPa) [2], large surface area (2600 m2/g),
high thermal conductivity (4.84 × 103–5.30 × 103 W/mK)
[3] and electrical conductivity (around 6000 S/m) [4], etc.
Even a low volume fraction of graphene is sufficient to
effectively improve the mechanical, electrical and thermal
* Ruchi Aradhana
aradhanaruchi@yahoo.com
1
Central Institute of Plastics Engineering & Technology
(CIPET), TVK Industrial Estate, Guindy, Chennai,
Tamil Nadu 600032, India
2
Laboratory for Advanced Research in Polymeric Materials
(LARPM), Central Institute of Plastics Engineering &
Technology (CIPET), Bhubaneswar, Odisha, India
of graphene (i.e. thermal or chemical reduction), chemical
reduction process through graphene oxide (GO) layers has
been most frequently researched route owing to their cost-
effectiveness [6], scalability and production in bulk quanti-
ties [1]. Typically, the graphene derivative produced by the
above-mentioned process termed as reduced graphene oxide
(rGO). rGO, a derivative of graphene with some structural
defects, considered as promising functional nanofiller for
electrically conductive adhesives (ECAs) due to their high
inherent electrical conductivity [7], excellent mechanical,
thermal, optical properties [8] and their ability for large-
scale production [9].
With the increasing demand for higher input/output
counts and miniaturization, various novel electronics pack-
aging materials are continuously being developed [10].
Although the development has been considerably advanced
over the past few decades, the vital requirements for the die
attach and interconnects among all the electronic compo-
nents remain unchanged [11]. The components should be
electrically connected to power, have high purity, fast curing
time, lower stress, high package crack resistance, etc [11,

13
Vol.:(0123456789)

12]. Therefore, polymer based ECAs are effectively replac-
ing the tin–lead solders owing to their advantages such as
environmental friendliness, lower processing temperature,
fewer processing steps, fine pitch capability, long service life
and lower cost, etc [11]. At the same time, more and more
functional materials at their nanoscale are being utilized in
electronic packaging applications for improving the adhe-
sion and electrical conductivity, such as i.e. carbon nano-
tubes (CNT) [13, 14], vapor grown carbon nanofiber and
graphene [15, 16], etc.
Conventionally, ECAs were fabricated by distributing
effective electrically conductive fillers throughout the insu-
lating thermosetting resins. Epoxy resins are a class of versa-
tile thermoset polymers widely used as conductive adhesives
in diverse fields such as electronic packaging. This includes
solder-less interconnections, display interconnections, com-
ponent renovation, die fittings [17]; and aerospace [18], etc.
Epoxy resin generally used as matrix material for adhesive
systems due to their high mechanical properties, outstanding
adhesion behaviour, excellent thermal and chemical resist-
ance [19], lower shrinkage [18] and acceptability of wide-
ranging additives and substrates [19], etc. There are a few lit-
eratures concerning epoxy/rGO conductive nanocomposites/
adhesives and their various applications [1, 5, 20]. Bindu
et al. [1] developed microwave exfoliated reduced graphene
oxide (MERGO) filled epoxy nanocomposites and witnessed
excellent AC conductivity (i.e. ­10−5 S/m) with the addition
of 5 wt% MERGO. Pokharel et al. [5] investigated the elec-
trical percolation threshold of epoxy composites incorpo-
rated with rGO. The rGO was synthesized by multi-step
microwave reduction of graphite oxide and the researchers
observed ­106.2 Ω/sq surface resistivity with 0.3 wt% RGO
filling. Yosefi et al. [20] prepared rGO/waterborne epoxy
(EP) composite through in situ polymerization and studied
electrical conductivity across in-plane and through-thick-
ness directions. The percolation threshold was found to be
0.12 vol%, while the conductivity was increased eightfold
when 0.5 wt% rGO was added. Sharmila et al. [21] examined
AC electrical conductivity of hybrid composites of epoxy
and reduced graphene oxide/iron oxide (RGO–Fe2O3), and
found maximum of ­10−4 S/m with 5 phr RGO–Fe2O3 loading
at 30 MHz frequency. Li et al. [15] studied the volume resis-
tivity of epoxy composite comprising of copper nanowires
(CuNWs) and rGO hybrid filler. They found that CuNWs/
NH2–rGO/epoxy exhibited lowest volume resitivity with a
value of 2.69 × 1011 Ω cm as compared to CuNWs/epoxy
and ­NH2–rGO/epoxy polymer composite. To the best of our
knowledge, no literature has been reported concerning rGO/
epoxy conductive adhesives with high volume fraction rGO
loading and their mechanical, electrical and thermal proper-
ties so far.
In the present work, epoxy conductive adhesives were
developed with the inclusion of rGO by varying wt% from
13
Journal of Materials Science: Materials in Electronics
10 to 50, and labelled as ­R10, ­R20, ­R30, ­R40, and ­R50. The
lap shear test of adhesive formulations was performed using
aluminium substrates for studying the adhesive strength.
The tensile strength and izod impact strengths (for notched
and unnotched specimens) were calculated for a detailed
examination of the mechanical properties of adhesive for-
mulations. The fractographic study of notched impact sam-
ples was investigated using scanning electron microscopy
(SEM) technique. The dispersion of rGO fillers within the
epoxy adhesive was visualized using transmission electron
microscopy (TEM). The directional electrical conductivity
(i.e. volume and surface conductivity) of adhesive samples
were inspected using super megaohmmeter and the thermal
conductivity ­(Tc) of conductive adhesives was studied by uti-
lizing the guarded hot plate method. The chemical structure
of rGO, nature of interaction between rGO and epoxy was
studied by Fourier transform infra‑red spectroscopy (FTIR).
The thermo-stability and thermal degradation temperature
of adhesive systems was examined by Thermo-gravimetric
analysis (TGA).
2 Materials and methods
2.1 Materials
Epoxy resin diglycidyl ether of bisphenol A (DGEBA),
Araldite GY250, Epoxy equivalent: 170–190 g/kg) and ali-
phatic amine curing agent (triethylenetetramine (TETA),
Aradur HY951, specific gravity: 0.98 g/cm3) were procured
from Huntsman Int Pvt. Ltd, Mumbai, India. The rGO with
avg. 4–8 no of layers, specific surface area: 180 m2/g and
99% purity was purchased from Platonic Nanotech Pvt. Ltd.,
India. Common chemical such as acetone was acquired from
Merck specialists Pvt. Ltd. India. The aluminium substrates
used for lap shear testing was purchased from Krishna
Homesmith Pvt. Ltd., India and cut in the dimension of
101.6 × 25.4 × 1.62 mm using CNC milling machine. All the
chemicals and materials were used as received for the fabri-
cation of adhesive formulations. The chemical structures of
DGEBA, TETA and rGO are shown in Fig. 1.
2.2 Fabrication of E–rGO conductive adhesives
To study the influence of rGO with high concentration in
the epoxy matrix, pristine epoxy adhesive (E), rGO filled
epoxy conductive adhesives with different wt% such as 10,
20, 30, 40 and 50 wt% (labelled as R­ 10, ­R20, ­R30, ­R40, ­R50)
were prepared. The composition of all epoxy-based adhe-
sive formulations are entered in Table 1 and the fabrication
method is illustrated in Fig. 2.
To secure proper dispersion, rGOs were initially dis-
persed in 30–40 mL of acetone using ultrasonication (6.5 L
Journal of Materials Science: Materials in Electronics

at room temperature for 7 days and further post-cured at

Fig. 1  Chemical structure of DGEBA epoxy resin, TETA, and rGO
capacity, M/s Deluxe Trading Co., India) for 30 min and con-
currently, DGEBA resin was kept in a vacuum oven at 35 °C
for around 30 min for avoiding trapped airs. The rGO and
acetone mixture was then mixed with the pristine DGEBA
resin utilizing an overhead stirrer (M/s Remi Electrotechnik
Ltd., Vasai) at 1000–1500 rpm for 60 min to ensure effective
mixing. Further, the mixture was subjected to ultrasonication
for 30 min to achieve thorough dispersion of rGO within the
base resin. The reaction mixture was then degassed in a vac-
uum oven for 30 min at 50 °C to conduct two activities such
as withdrawing air bubbles and evaporating the remaining
acetone. Lastly, the curing agent was mixed with the result-
ing mixture for 5–11 min by retaining 100:13 w/w epoxy
resin: curing agent ratio. The mixture was applied to alumin-
ium substrates and poured into a metallic mould, then cured
with the following curing procedure such as first at ambient
temperature for 1 day and s, for post-curing at 80 °C for 4 h
[19]. Various researcher groups have been utilized different
types of method of preparation for epoxy/rGO composites.
For instance, Lin et al. [22] reported regarding the prepara-
tion of epoxy coatings by incorporating a composite filler
[poly(styrenesulfonate)–polyaniline/reduced graphene oxide
(PSS–PANI/rGO)] and rGO. The authors first blended the
bisphenol-A type epoxy resin with various amounts of rGO
or PSS–PANI/rGO by utilizing a tri-roller mill. Then, the
curing agent was added into the above mixture by mechani-
cal agitation while maintaining the weight ratio of 11:20
(for curing agent: epoxy). Subsequently, they were cured
100 °C for 1 h and another 1 h at 130 °C. Che et al. [23] fab-
ricated graphene oxide sheets–zirconia spheres ­(ZrO2–rGO)
nanohybrids as a reinforcement for epoxy composites. They
have prepared the Z ­ rO2–rGO/epoxy composites by following
procedure: first the epoxy monomer was heated at 60 °C in
a drying oven. The Z ­ rO2–rGO was first dispersed in acetone
with the integrated high-shear mixing and followed by ultra-
sonication. Then mixed with the epoxy oligomer at 80 °C
with vigorous stirring for 30 min. For removal of bubbles,
the above mixture then intensely stirred for 2 h at 60 °C
under ultrasonic surroundings. Afterwards, a stoichiometric
amount of DDM (curing agent) was mixed thoroughly by
stirring for 1 h at 60 °C. Then the mixture was degassed in
a vacuum oven for 30 min at 60 °C. Finally, the mixture was
poured into a preheated mould and cured at 100 °C for 2 h,
followed by further heating at 150 °C for 2 h. As the afore-
mentioned researchers used composite or nanohybrid fillers
as the reinforcement for epoxy composites, it is essential to
follow additional processes for effective dispersion of fill-
ers and complete curing of the composites. However, in this
work, single filler i.e. rGO was used as a reinforcement to
enhance the performance of epoxy adhesives.
3 Characterizations
3.1 Lap shear test
The adhesive strength for unmodified epoxy and epoxy con-
ductive adhesives was determined by performing lap shear
test of two aluminium substrates (101.6 × 25.4 × 1.62 mm
dimension) bonded together with 12.7 mm overlapped area
as per ASTM D-1002. The tests were performed by utilizing
the Universal testing machine (UTM, 3382 Instron Instru-
ments Ltd, UK) with a crosshead speed of 1.27 mm/min for
around five samples and mean result was recorded.

Table 1  Various epoxy-based Coding Sample Quantity (g) Acetone (mL)

adhesives composition
Epoxy resin Curing agent rGO

E Epoxy 130 13 – –
R10 Epoxy–10 wt% rGO 119 13 11.90 30
R20 Epoxy–20 wt% rGO 108 13 21.60 30
R30 Epoxy–30 wt% rGO 100 13 30 30
R40 Epoxy–40 wt% rGO 93 13 37.2 35
R50 Epoxy–50 wt% rGO 87 13 43.50 40

13

Fig. 2  Schematic diagram for the fabrication of E–rGO conductive adhesive systems
3.2 Tensile test
The tensile strength, elongation at break and modulus for
E and ­R10–R50 adhesive systems were studied at 1 mm/
min crosshead speed using the Universal testing machine
(UTM, LR-100NK, 3382 Instron Instruments Ltd, UK) in
accord with ASTM D-638 standard. The specimens with
the length of 33  mm, grip area of 18.7  mm and thick-
ness of 3 mm were cut by CNC cutter and mean value
was reported after testing at least five samples of each
adhesive.
3.3 Impact test
Impact strength (for both notched and unnotched speci-
mens possess 64.5 × 12.7 × 3.2 mm dimension) for unmod-
ified epoxy and E–rGO adhesive formulations were cal-
culated according to the standard of ASTM D-256 by
13
Journal of Materials Science: Materials in Electronics
utilizing an Impact tester, (IT 504 Plastic Impact, M/s
Tinius Olsen, USA).
3.4 Scanning electron microscopy (SEM)
The fractography evaluation of E, R­ 10, ­R30 and R
­ 50 adhesive
formulations later izod impact testing for notched specimens
was analyzed with 5 keV accelerating voltage and 50 µm
scale bar by employing SEM (EVO MA15, M/s Carl Zeiss
SMT, Germany). The notched impact samples were sputter
coated by Au/Pd mixture (to avoid electric discharge) before
the analysis.
3.5 Transmission electron microscopy (TEM)
TEM (JEM-1400, JEOL, Japan) for E–rGO conductive adhe-
sive formulation was used to study the extent of dispersion
of rGO layers in the epoxy matrix with 80–100 KeV accel-
erating voltage. The samples were prepared as an ultra-thin
Journal of Materials Science: Materials in Electronics
section using Leica microtome and placed on a copper grid
prior to TEM imaging.
3.6 Electrical conductivity
The electrical conductivity [volume (σv) and surface (σs)]
for epoxy based conductive adhesive systems compared with
unmodified epoxy was determined in accord with ASTM
D-257 standard (employing 100 mm diameter and 3 mm
thick round disk) by utilizing Super megaohmmeter (SM-
8220, M/s TOA Electronics Ltd, Japan).
3.7 Thermal conductivity
The thermal conductivity of E and ­R10–R50 adhesive formu-
lations was measured by following guarded hot plate method
according to ASTM E-1530 standard and using Thermal
conductivity tester (Unitherm 2022, M/s Anter Corpo,
USA). A circular disk with a diameter of 50 mm and thick-
ness of 3 mm for each adhesive formulation was evaluated
over four varying temperatures of 35, 55, 75 and 95 °C.
3.8 FTIR spectroscopy
FTIR spectra were examined to study the functional groups
of rGO along with to explore the nature of interaction
between the rGO filler and the epoxy matrix. The samples
were scanned over 4000 to 400 cm−1 wavelength by using
Continuum Nicolet 6700, M/s Thermo Electron Corpora-
tion, USA.
3.9 Thermo‑gravimetric analysis (TGA)
The thermo-stability and thermal degradation temperature
for cured E and ­R30 adhesive systems were analysed by
using TGA (Q-50, M/s TA Instruments, USA). The 6–10 mg
weight samples were heated over 30–800 °C temperature
range at a 10 °C/min heating rate as per ASTM E-1868
standard.
4 Results and discussion
4.1 Lap shear test
The shear stress versus shear strain curves of the epoxy and
its conductive adhesives with varying wt% of rGO are rep-
resented in Fig. 3a. The shear strength and different failure
modes of E and R ­ 10–R50 adhesive formulations are listed in
Table 2. Figure 3b–g depicts the failure mode of all adhesive
formulations which reveal transition from adhesive failure
to partially or fully cohesive failure.
The shear strength of epoxy resin unveils noticeable incre-
ment when rGO layers are inserted within the unmodified
epoxy resin. This increasing trend endures up to a pleatue
(i.e. 40 wt% rGO), afterward decreases with higher rGO con-
tent. The E exhibited 5.43 MPa shear strength and adhesive
failure mode which usually causes by the adherent-adhesive
interface fracture (shown in Fig. 3b). When rGO incorpo-
rated with varying wt% i.e. 10, 20, 30 and 40 wt%, the shear
strength substantially increased by about 18%, 22.3%, 45%
and 72.8% in comparison to the base epoxy. In comparison
to the ­R40 adhesive formulation, the ­R50 adhesive possessed
shear strength of 6.08 MPa which is 35% lower. In addi-
tion, the failure mode of all conductive adhesives is modified
from adhesive to partially cohesive or fully cohesive failure
as indicated by Fig. 3c–g. This modification of failure modes
signifies better bonding efficiency of conductive adhesives
after rGO inclusion. Similar trends have been detected in our
previous paper [19] and by Singh et al. [24, 25] with rein-
forcement of different nanomaterials. The improvement of
shear strength can be imputed to the good interfacial interac-
tion between the rGO and the epoxy resin owing to (i) the
covalent bonding of oxygen functional groups of rGO with
epoxide group of DGEBA resin and (ii) large surface area
of rGO layers. This leads to effective load transfer between
matrix and filler resulting in higher cohesion strength of
the adhesive formulations with Al substrates. Similar type
results have been noticed by Kumar et al. [26] and Norhakim
et al. [27]. The diminution of shear strength at higher rGO
content can be credited to the incompatible dispersion. As
the filler content increases, the resin viscosity also increases
simultaneously decreasing the flow rate of epoxy resin. This
decreased flow rate develops the micro-voids which sub-
sequently deteriorates the shear strength of the adhesive.
Similar findings have been witnessed by Adak et al. [28]
in the case of thermally reduced graphene oxide reinforced
woven carbon fiber/epoxy composite.
4.2 Tensile test
The mechanical performance examined through tensile tests
including tensile strength, tensile modulus, and elongation at
break are summarized in Table 3 and respective stress versus
strain graphs are presented in Fig. 4.
From Table 3, it is clearly witnessed that the rGO inclu-
sion into the epoxy resin resulted in lower tensile strength
than that of the base resin. The tensile strength of pristine
epoxy was found to be 47.45 MPa. When rGO particles
are incorporated, the tensile strength decreased by around
33%, 26.4%, 11%, 35% and 36.4% for R ­ 10, ­R20, ­R30, ­R40
and ­R50 adhesive formulations as compared to unmodi-
fied epoxy. The diminution can be imputed to the altera-
tion of the stoichiometric ratio between epoxide groups
of DGEBA resin and amine groups of TETA by the rGO
13
 Journal of Materials Science: Materials in Electronics

Fig. 3  a Shear stress versus

strain graphs of E and ­R10–R50
adhesive formulations; Different
failure modes of b E, c ­R10, d
­R20, e ­R30, f ­R40, g ­R50

Table 2  Adhesive strength (lap shear strength) and different failure Table 3  Tensile properties of E and ­R10–R50 conductive adhesive for-
modes of epoxy adhesive with various wt% of rGO mulations
Sample Shear strength (MPa) Failure mode Sample Tensile strength Tensile modulus Elongation
(MPa) (MPa) at break (%)
E 5.43 ± 0.86 Adhesive
R10 6.41 ± 0.74 Partially cohesive E 47.45 ± 7.2 2624.62 ± 79 1.57 ± 0.92
R20 6.64 ± 0.91 Partially cohesive R10 31.74 ± 8.1 3148.26 ± 86 1.32 ± 0.72
R30 7.88 ± 0.63 Partially cohesive R20 34.91 ± 6.5 3565.74 ± 63 1.43 ± 0.81
R40 9.38 ± 0.82 Fully cohesive R30 42.13 ± 7.9 2851.48 ± 74 2.39 ± 0.67
R50 6.08 ± 0.97 Partially cohesive R40 31.05 ± 5.4 3577.30 ± 92 1.26 ± 0.78
R50 30.17 ± 6.2 3751.95 ± 66 1.13 ± 0.70

content which eventually participates in crosslinking

reaction and disturbs the curing process of epoxy resin
[29].The ­R 10 adhesive formulation exhibit 31.74  MPa
tensile strength. The tensile strength of adhesive sys-
tems increased gradually up to 30 wt% rGO inclusion and
afterwards decreased with higher rGO loading (i.e. 40
and 50 wt%). In comparison to the R ­ 10 system, the ten-
sile strength of ­R20 and ­R30 adhesives were improved by
about 10% and 33%, respectively. However, the strength of
adhesives comprising 40 and 50 wt% rGO were diminished
by 2.21% and ~ 5% as compared to ­R10 adhesive formula-
tion. The higher tensile strength of R
­ 20–R30 adhesive sys-
tems can be clarified by studying the possible interactions
between DGEBA resin, rGO and TETA as illustrated in
Scheme 1. The oxygen functional groups present on the

13
Journal of Materials Science: Materials in Electronics
Fig. 4  Tensile stress–strain graphs of E and ­R10–R50 conductive adhe-
sives
surface of rGO is susceptible to reaction with epoxy resin
by opening the ring of epoxide group. Further, the epoxy
resin reacts with amine group of TETA and simultane-
ously, the oxygen group of rGO also form chemical bonds
with TETA which develop a 3D cross-linked structure.
Hence, this leads to higher tensile strength of adhesive
systems. The similar type findings have been detected by
Galicia et al. [29] with combined GO and rGO filler. How-
ever, the lower tensile strength of R ­ 40 and ­R50 adhesive
formulations can be ascribed to the formation of clusters
or aggregates of overloaded rGO particles that behave
as stress concentrators and lead to early rupture. Similar
behaviour has been observed by other researchers [26, 27,
30].
As obvious from Table  3, the tensile modulus of
­R 10–R 50 adhesive formulations showed contrary results
than that of their tensile strength values. With addition of
10 to 50 wt% rGO particles, the modulus extended up to
3148, 3566, 2851, 3577 and 3752 MPa which are around
20%, 36%, 9%, 36% and 43% higher than that of pristine
epoxy (i.e. 2625 MPa). The improved tensile modulus of
­R 10–R 50 adhesive formulations can be attributed to the
immobilization of epoxy chains which is created by the
rGO layers with their platelet geometry. Thus, provided the
reinforcing effect and enhanced the modulus. Equivalent
findings have been noticed by Chhetri et al. [30]. The elon-
gation at break for conductive adhesive systems ­(R10–R20
and ­R 40–R 50) followed similar response except for R ­ 30
system. With the incorporation of rGO particles into the
base resin, the elongation at break diminished which can
be ascribed to the higher aspect ratio of rGO layers and
interaction between the epoxy resin and rGO particles,
that impedes the polymer chain movements and as a con-
sequence lowers the elongation [31].
4.3 Impact test
To study the reinforcing effect of rGO with varying content
(i.e. high wt%) on epoxy adhesives, izod impact strength (for
unnotched and notched samples) were calculated and listed
in Table 4. The variation of impact strength for adhesive
systems versus rGO concentration is plotted in Fig. 5.
The unnotched and notched impact strength of all adhe-
sive formulations follow similar trend as indicated in Fig. 5.
The rGO introduction to the epoxy adhesive formulation
increases the izod impact strength, both unnotched and
notched strength up to a plateau (i.e. 30 wt% rGO content)
and then decreases with higher concentration as shown in
Table 4. The epoxy adhesive exhibited unnotched impact
strength of 6.53 kJ/m2. The strength increased to 7.34, 8.68
and 9.87 kJ/m2 with the addition of 10, 20 and 30 wt% of
rGO which are about 12%, 33% and 51% higher in compari-
son to pure epoxy. However, when the content of rGO was
increased to 40 and 50 wt%, the unnotched impact strength
diminished by approx. 21% and 32%, respectively as com-
pared to ­R30. The impact strength for unnotched samples
decreased for R­ 40 and R
­ 50 but still higher than that of pristine
epoxy. The enhancement of unnotched impact strength can
be due to the reinforcing effect of rGO that provide tough-
ness to the matrix. The volume fraction of rGO increased
with the addition of rGO particles, resulting in higher load
transfer from matrix to rGO which eventually increases the
cross-linking of adhesive formulations. This leads to higher
unnotched impact strength which has also been noticed by
Li et al. [32]. The decrement can be assigned to the lower
dispersibility of rGO within the base resin when higher rGO
content was present, that leads to agglomerated clusters.
The notched impact strength of epoxy resin (1.25 kJ/
m2) was improved by around 54%, 70% and 100% with
the incorporation of 10, 20 and 30 wt% rGO. This can be
explained with the following arguments: As rGO embraces
many oxygen functional groups on its surface, it possesses
higher compatibility with the epoxy resin and curing agent
which promotes effective dispersibility throughout the resin
(as shown in SEM images, Fig. 6b,c). The larger surface
area of rGO significantly increases the toughness of adhesive
systems which is stated as another reason for impact strength
improvement. Similar behaviour has also been witnessed
by Tang et al. [33] for GO/epoxy nanocomposites. How-
ever, when the rGO amount increased to 40 and 50 wt%, the
notched impact strength decreased by nearly 34% and 40%
while reaching a value of 1.65 and 1.49 kJ/m2 as compared
to ­R30 adhesive system (2.50 kJ/m2). The diminution can be
due to the immoderate interfacial contacts (as represented in
SEM micrograph of ­R50: Fig. 6d) between both the rGO/rGO
layers and rGO/epoxy matrix, that diminished the notched
impact strength. Similar findings have also been detected
by Lee et al. [34].
13

Scheme 1  Illustrative diagram
for possible interactions
between DGEBA epoxy resin,
rGO and TETA curing agent
4.4 Scanning electron microscopy (SEM)
To examine the interfacial adhesion between rGO and epoxy
resin extensively, the fractured surfaces of notched impact
samples for all adhesive formulations were visualized by
using SEM as shown in Fig. 6.
From Fig. 6, it can be clearly visible that unmodified
epoxy adhesive represented a brittle fracture (as shown in
Fig. 6a) with the smooth and clear surface along with some
13
Journal of Materials Science: Materials in Electronics
river-like profiles. This result demonstrates the lower frac-
ture toughness and impact strength of unmodified epoxy
resin during impact failure. Similar behaviour has also
been witnessed in our previous paper [35] and by Singh
et al. [24, 25]. On the other hand, all the E–rGO conduc-
tive adhesives showed rough or coarser fracture surfaces as
the rGO content increases. In addition, the fracture zones
generated in various orientations, which may be triggered
due to the random dispersion of rGO layers within the
Journal of Materials Science: Materials in Electronics

Table 4  Impact strength of E and E–rGO adhesive formulations 4.5 Transmission electron microscopy (TEM)
Sample Un-notched impact strength Notched impact
(kJ/m2) strength (kJ/m2) The morphology and dispersion level of rGO layers in the
­R30 adhesive formulation was evaluated by TEM for cor-
E 6.53 ± 2.86 1.25 ± 0.58
roborating the higher electrical conductivity of the system.
R10 7.34 ± 2.95 1.92 ± 0.62
Figure 7 represents the TEM images of the ­R30 system at
R20 8.68 ± 3.08 2.12 ± 0.74
different magnification levels.
R30 9.87 ± 3.16 2.50 ± 0.55
From TEM micrographs (Fig. 7 a, b), it is clear that the
R40 7.82 ± 2.74 1.65 ± 0.68
black or grey hair-like structures indicate the cross-sectional
R50 6.71 ± 3.12 1.49 ± 0.83
portions of rGO layers. The rGO layers are dispersed homo-
geneously or uniformly throughout the epoxy matrix (as
indicated by red arrows) along with small aggregates (as
highlighted by yellow arrows). The individual or ultra-thin
layer seems transparent, while stacked layers of rGO appear
dark in colour. The uniform dispersion or exfoliation of rGO
layers is because of the interfacial interactions between the
epoxy resin and oxygen functional groups of rGO sheets
[1]. The TEM images showed the edges of rGO layers are
overlapping with each other, constructing efficient electri-
cal pathways within the epoxy matrix, which ultimately
improved the electrical conductivity of the adhesive system.
As rGOs are the stacked layers of GO after removal of oxy-
gen functionalities upon reduction process, they possess less
number of functional groups and can construct conductive
paths for electron transport. Hence, this indicates the reason
for higher electrical conductivity of R ­ 30 adhesive system.
Fig. 5  Unnotched and notched impact strength variation of conduc- Similar behaviour has also been noticed by Sun et al. [37].
tive adhesives against rGO loading
4.6 Electrical conductivity
epoxy matrix [36]. In the case of R
­ 10 and R
­ 30 adhesive for-
mulations, the rGO layers seem to be thoroughly dispersed The electrical conductivities of adhesive formulations as a
in the matrix, as agglomerated clusters aren’t encountered function of rGO loading along two directions i.e. through-
in Fig. 6 b, c. This suggests that rGO layers are tightly the-thickness (volume conductivity, σv) and in-plane (sur-
embedded in the epoxy resin with negligible cleavages face conductivity, σs) are listed in Table 5 and log curves of
around rGO layers, which reveals strong interfacial adhe- electrical conductivities are shown in Fig. 8.
sion/interactions between the rGO layer and epoxy matrix. The volume and surface conductivity of unmodified
Hence, the dispersed rGO layers block the easy crack prop- epoxy adhesive was found to be gradually increasing with
agation leading to higher impact strength of R ­ 10 and R
­ 30 the addition of rGO from 10 to 50 wt%. The epoxy resin
systems than that of the R­ 50 adhesive system. However, possessed volume and surface conductivity of 1.13 × 10−13
as shown in Fig. 6 d, the R ­ 50 adhesive system exhibits S/m and 2.35 × 10−11 S, respectively which evidence insu-
aggregated structures (as highlighted by red circles) which lating characteristics of the epoxy material. In the case of
can be due to the Van der Waals forces within the planar E–rGO conductive adhesives, the σv values reached from
geometries of rGO layers. The aggregated clusters behave 1.13 × 10−13 S/m to 1.09 × 10−12, 7.35 × 10−12, 2.28 × 10−11,
as stress concentrators and promote fracture around it, 1.37 × 10−08 and 3.44 × 10−08 S/m for R ­ 10, ­R20, ­R30, ­R40
resulting in lower impact strength. As described by Liu and ­R50 adhesives which are around one, one, two, five
et al. [36], crack bowing or crack pinning mechanism is and five order of magnitude, respectively higher than that
a usually-known toughening mechanism that simplifies of epoxy adhesive. In addition, the σs of ­R10–R50 conduc-
the reason of higher impact strength for rGO filled epoxy tive adhesives enhanced by one, four, four, five and fivefold
adhesive systems. After addition of stiff and rigid rGO with 1.05 × 10−10, 1.48 × 10−07, 6.85 × 10−07, 2.89 × 10−06
layers in the epoxy matrix, the crack fronts may bow or and 8.54 × 10 −06 S values as compared to pure epoxy
pinned or it may deflect from its original path generat- (2.35 × 10−11 S). Therefore, the electrical percolation thresh-
ing secondary cracks. Thus, require more energy for crack old (EPT) for E–rGO conductive adhesives was determined
propagation and results in improved impact strength. to be at 40 and 20 wt% of rGO loading in the case of σv

13
 Journal of Materials Science: Materials in Electronics

Fig. 6  SEM images a E, b ­R10, c ­R30 and d ­R50 adhesive formulations. (Color figure online)

Fig. 7  a, b TEM micrograph of ­R30 adhesive formulation at different magnification. (Color figure online)

and σs, respectively. When 40 wt% rGO was included, the
σv value improved abruptly by five order of magnitude,
while the σs showed subsequent increase of four order with
20 wt% addition as compared to unmodified epoxy. Hence,
the EPT is known as the critical filler concentration, at which
the electrical conductivity increases abruptly and then fol-
lowed by a steady increment. The EPT is an indication for
the formation of 3D conductive network within the insu-
lating polymer matrix. As noticeable from Table 5, the in-
plane conductivity for conductive adhesives is higher than

13
Journal of Materials Science: Materials in Electronics

Table 5  Volume and surface conductivity of E and E–rGO adhesive Table 6  Thermal conductivity of E and R
­ 10–R50 adhesive systems
formulations
Sample Thermal conductivity (W/mK)
Sample Volume conductivity (σv) Surface con-
(S/m) ductivity (σs) 35 °C 55 °C 75 °C 95 °C
(S)
E 0.185 0.21 0.228 0.24
E 1.13 × 10−13 2.35 × 10−11 R10 0.32 0.35 0.36 0.39
R10 1.09 × 10−12 1.05 × 10−10 R20 0.44 0.46 0.48 0.51
R20 7.35 × 10−12 1.48 × 10−07 R30 0.61 0.64 0.66 0.67
R30 2.28 × 10−11 6.85 × 10−07 R40 0.83 0.85 0.86 0.89
R40 1.37 × 10−08 2.89 × 10−06 R50 0.94 0.95 0.97 0.98
R50 3.44 × 10−08 8.54 × 10−06

Fig. 8  Log curves of electrical conductivity (σv & σs) of epoxy and

Fig. 9  Thermal conductivity of epoxy based adhesive formulations as
conductive adhesive formulations
a function of rGO concentration

through-the-thickness conductivity, revealing the effective
maintenance of electrical contacts between the adjacent rGO
layers along in-plane direction than in through-the-thickness
direction. Same behaviour has also been observed in our
previous paper [19] and by Yosefi et al. [38, 39]. The elec-
trical conductivity increment with the addition of rGO can
be ascribed to the construction of electrical pathways by the
rGO layers throughout the epoxy matrix which convert the
insulating epoxy into a conductive material. The electrical
paths formation can be understood with the following two
reasons: (a) the interactions between the rGO layers and
epoxy resin (π–π interactions) and between the rGO–rGO
layers which leads to the generation of highly dense rGO
percolation networks [40, 41]. This can be confirmed by
SEM images (Fig. 6b–d) of conductive adhesives. (b) due to
the larger surface area of rGO sheets, the edges can be easily
overlapped with each other forming conductive paths along
with lower contact resistance as shown in Fig. 7a,b [37].
The electron transfer within the conductive adhesives can
be explained with the following mechanisms: (a) electron
tunnelling between the adequately close rGO layers. As the
rGO layers are segregated by a narrow layer of epoxy, the
electron can tunnel through adjacent rGO layers. (b) direct
contacts between the rGO layers- when the rGO concentra-
tion increases, they physically contact one another and forms
a conductive network for electron transfer [39].
4.7 Thermal conductivity
The thermal conductivity values of E and ­R10–R50 adhe-
sive formulations at various temperatures were studied. The
obtained ­Tc values are tabulated in Table 6 and illustrated
in Fig. 9.
The thermal conductivity values of unmodified epoxy
and conductive adhesive systems exhibited similar trend,
such as T­ c increased with the temperature increment from
35 to 95 °C. The increasing trend of ­Tc with temperature is
ascribed to the expansion of polymer matrix which dispersed
the rGO layers for constructing the conductive network. As
the temperature increases, the rGO layers compressed with
one another start to disperse thoroughly within the matrix,
which form the conductive network resulted in T ­ c improve-
ment owing to the expansion of polymer matrix [19].

13

With the addition of rGO particles, the ­Tc values of
conductive adhesives followed an improving tendency as
observed from Table 6. At 35 °C, the T ­ c increases from
0.185 W/mK for E to 0.32 for ­R10, 0.44 for R ­ 20, 0.61 for
­R 30, 0.83 for ­R 40 and 0.94 W/mK for ­R 50 adhesive sys-
tems which are an increase of around 73%, 138%, 230%,
349% and 408%, respectively. Additionally, in comparison
to ­Tc value for E at 95 °C, the ­Tc improved by about 63%,
113%, 179%, 271% and 308% for ­R10, ­R20, ­R30, ­R40 and
­R50 adhesive systems, respectively. The improvement of
­Tc values with the inclusion of rGO particles can be inter-
preted as follows: (a) the intrinsic T
­ c and thin layer struc-
ture of rGO can certainly form a 3D thermal conductive
network within the epoxy matrix as can be observed from
SEM images, Fig. 6b–d. The 3D network of rGO layers
can effectively transport heat within the epoxy matrix and
increases the ­Tc value [42]. (b) As high content of rGO
particles were used, the inter-particle spacing decreases
and as a result mean free path between the rGO layers for
phonon transfer also decreases. This leads to the formation
of conductive network with particle–particle contact and
improves the ­Tc of adhesive. Similar findings have also
been detected by Olowojoba et al. [43]. (c) The residual
functional groups present on the planar geometry of rGO
furnished a better compatibility with epoxy resin. Addi-
tionally, the functionalities can behave as a bridge between
the rGO layers and epoxy resin, which may diminish the
contact resistance and enhance the ­Tc values of adhesive
formulations. Similar discussion has also been reported
by Tang et al. [44].
Fig. 10  FTIR spectra of rGO particles, E and R
­ 30 adhesive systems
13
Journal of Materials Science: Materials in Electronics
4.8 FTIR spectroscopy
Figure 10 depicts the FTIR spectra of rGO filler along with
the E and ­R30 adhesive systems. The spectrum for rGO
unveils the characteristics peaks while E and R­ 30 systems dis-
played almost identical behaviour. The IR spectrum of rGO
reveal two eminent peaks at 1712.4 cm−1 can be appointed
to the stretching vibration of C=O and at 1058.1 cm−1 can
be designated as C–O stretching vibration, proclaiming the
existence of few oxygen functional groups susceptible to
react with DGEBA resin or TETA as illustrated in Scheme 1
[45]. The major transmittance peaks of unmodified epoxy
adhesive (as shown in Fig. 10) are at 3378.8 cm−1 for O–H
stretching vibration, at 2926.8 and 2862.8 cm−1 ascribed
to asymmetric and symmetric C–H stretching vibration
respectively, at 1723.3 cm−1 due to C=O stretching, at 1412,
1382.7 and 1292.4 cm−1 (for in-plane bending vibrations of
–OH groups), at 1241.6 cm−1 designated for epoxy group, at
1179.9 cm−1 (due to C–O–C asymmetric stretching vibration
for ester), at 1030.8 cm−1 ascribed to aromatic C–O stretch-
ing vibration and the most intensive peak at 825.2 cm−1 can
be appointed to the oxirane group of epoxy resin [18, 46]. In
the case of R ­ 30 adhesive system, IR spectra showed a lower
intensity peak at 1714.5 cm−1 which is in-between the peak
of rGO (1712.4 cm−1) and E adhesive (1723.3 cm−1). Fur-
ther, the peak for oxirane group of epoxy at 825.2 cm−1 (for
epoxy resin) shifted to a lower wavenumber i.e. 798.5 cm−1
indicate the effective interaction of rGO with epoxy matrix.
Similar findings have also been detected by Singh et al. [18].
Table 7 summarizes the major functional groups of E and
­R30 adhesive systems along with functional groups of rGO
filler.
4.9 Thermo‑gravimetric analysis (TGA)
To examine the influence of rGO filler on the thermal deg-
radation behaviour and stability of epoxy resin, TG analysis
Table 7  Detail of functional groups of rGO and a comparison of
major functional groups of E and ­R30 adhesive systems
Functional groups Characteristics transmittance (ν,
­cm−1)
rGO E R30
O–H stretching – 3378.8 3367.1
CH2 (asymmetric stretching) – 2926.8 2925.9
CH2 (symmetric stretching) – 2862.8 2864.3
Asymmetric C═O stretching 1712.4 1723.3 1714.5
Asymmetric C–O–C stretching – 1179.9 1177.6
C–O stretching 1058.1 – –
Aromatic C–O stretching – 1030.8 1009.3
Epoxy group – 825.2 798.4
Journal of Materials Science: Materials in Electronics
Fig. 11  a TGA and b DTG thermograms of E and ­R30 adhesive formulation
was conducted and the corresponding TGA and DTG ther-
mograms are depicted in Fig. 11a,b. The obtained param-
eters from TGA and DTG curves such as 10% weight loss
temperature ­(T10%), 50% weight loss temperature (­ T50%), first
degradation temperature (­ Tonset), maximum degradation tem-
perature ­(Td(max)), final degradation temperature ­(Tendset) and
% weight remaining at 650 °C ­(CR650) are summarized in
Table 8.
The TGA graphs as depicted in Fig. 11a denoted two
stage degradation process for base epoxy adhesive whilst
­R30 system showed one-stage degradation profile. The first
stage degradation of E where major weight loss occurred
at around 270–365 °C that can be due to the main epoxy
chain pyrolysis and the second stage about 475–660 °C can
be attributed to the decomposition of epoxy network after
curing [19]. Similar trends have also been noticed by other
researchers [25, 35]. However, the R ­ 30 system exhibited
one step degradation in the range of 260–380 °C with sig-
nificant weight loss and afterwards the formation of char
residue. Addition of 30 wt% rGO within the epoxy resin
increased both ­T10% and ­T50% by 4 °C and 5 °C, respectively
as compared to virgin epoxy. Further, the T ­ onset which nar-
rates the first degradation temperature of adhesive system
and ­Td(max) showed 14 °C and 10 °C increment over epoxy
resin. As the R­ 30 adhesive system displayed single step deg-
radation profile, the ­Tendset value diminished by 211 °C than
that of base line epoxy. Therefore, it can be clearly noticed
from insert of Fig. 11a that ­R30 adhesive system possessed
higher thermo-stability as compared to epoxy resin. This
can be ascribed to the ‘tortuous path effect’ of rGO layers
Table 8  TGA and DTG data of Samples T10% (°C)
E and ­R30 adhesive systems
E 331
R30 335
which behaves as barrier and detains the degradation of
epoxy matrix. As shown in Fig. 7 (TEM images), the rGO
layers attain an effective dispersion throughout the epoxy
matrix which can easily hinder the segmental movement of
epoxy chains in-between them while delaying their volatile
decomposition [19]. In addition, due to the strong interfacial
interaction between rGO and DGEBA resin (as illustrated
in Scheme 1), leads to higher crosslinking density network
and concluded in higher degradation temperature [30]. The
% weight remained at 650 °C for ­R30 adhesive system was
found to be substantially higher i.e. 25.7% as compared to
unmodified epoxy resin. When the epoxy resin is reinforced
with the rGO filler, results in higher char retention that can
be attributed to the existence of carbon net structure which
impedes the generation of gaseous product [47].
5 Conclusion
In the present study, an attempt has been done to prepare an
electrically conductive epoxy adhesive filled with the high
content of rGO (i.e. 10–50 wt%). The lap shear test was
performed to study the adhesive strength of epoxy-based
adhesive systems. The test results revealed that adhesive
with 40 wt% rGO possessed highest shear strength which
is 72.8% higher over unmodified epoxy. While the tensile
test results showed a decrement of 33% in tensile strength
even with the introduction of 10 wt% rGO. The unnotched
and notched impact strength of epoxy resin found to be
increasing up to 51% and 100% respectively, when 30 wt%
T50% (°C) Tonset (°C) Td(max) (°C) Tendset (°C) CR650 (%)
368 271 343 662 0.3
373 285 353 451 26
13

rGO was incorporated within the matrix. The fractography
analysis of notched impact samples was examined by SEM
and unveils that crack pinning is the toughening mechanism
for E–rGO adhesive systems. The dispersion assessment of
rGO within the epoxy matrix was visualized by TEM tech-
nique, revealing the effective distribution of rGO in epoxy
matrix. The volume and surface conductivity was increased
up to 3.44 × 10−08 S/m and 8.54 × 10−06 S with 50 wt% rGO
addition, which are five and five-fold higher in compari-
son to the epoxy resin. At 35 °C, the T ­ c was enhanced by
~ 408% as compared to pristine epoxy, when 50 wt% rGO
was included. FTIR spectra was used to study the nature of
interaction between rGO and epoxy matrix. The adhesive
systems showed higher thermo-stability with the introduc-
tion of rGO as detected by TGA technique.
References
1. T.K.B. Sharmila, A.B. Nair, B.T. Abraham, P.M.S. Beegum, E.
Thomas, Polymer (Guildf) 55, 3614 (2014)
2. H. Feng, X. Wang, D. Wu, Ind. Eng. Chem. Res. 52, 10160 (2014)
3. X. Zhang, O. Alloul, Q. He, J. Zhu, M. Joseph, Y. Li, S. Wei, Z.
Guo, Polymer (Guildf) 54, 3594 (2013)
4. Z.A. Ghaleb, M. Mariatti, Z.M. Ariff, Composites A 58, 77 (2014)
5. P. Pokharel, Q. Truong, D.S. Lee, Composites B 64, 187 (2014)
6. G. Tang, Z. Jiang, X. Li, H. Zhang, S. Hong, Z. Yu, Composites
B 67, 564 (2014)
7. Graphenea, Reduced Graphene Oxide: Properties, Applications
and Production Methods. (2015). https​://www.azona​no.com/artic​
le.aspx?Artic​leID=4041. Accessed 10 May 2018
8. M. Lundie, Z. Sljivancanin, S. Tomic, J. Mater. Chem. C 3, 7632
(2015)
9. J.M. Vazquez-moreno, V. Yuste-sanchez, R. Sanchez-hidalgo, R.
Verdejo, Eur. Polym. J. 93, 1 (2017)
10. H. Fan, M.M. Yuen, Nanopackaging (Springer, Cham, 2008),
pp. 39–59
11. G.Y. Li, C.P. Wong, Micro-and Opto-Electronic Materials and
Structures, vol 2, (Springer, New York, 2007), pp. B611–B627
12. S. Takeda, T. Masuko, N. Takano, T. Inada, Materials for
Advanced Packaging, (Springer, Cham, 2017), pp. 469–510
13. B.S. Yim, B.H. Lee, J. Kim, J.M. Kim, J. Mater. Sci.: Mater.
Electron. 25, 5208 (2014)
14. B.S. Yim, J.M. Kim, J. Mater. Sci.: Mater. Electron. 26, 1678
(2015)
15. M. Li, C. Tang, L. Zhang, B. Shang, S. Zheng, J. Mater. Sci.:
Mater. Electron. 28, 15694 (2017)
16. J. Kim, B. Yim, J. Kim, J. Kim, Microelectron. Reliab. 52, 595
(2012)
17. E. Sancaktar, L. Bai, Polymer (Basel) 3, 427 (2011)
18. A.K. Singh, B.P. Panda, S. Mohanty, S.K. Nayak, M.K. Gupta,
Polym. Adv. Technol. 28, 1851 (2017)
19. R. Aradhana, S. Mohanty, S.K. Nayak, Polymer (Guildf) 141, 109
(2018)
13
View publication stats
Journal of Materials Science: Materials in Electronics
20. N. Yousefi, X. Lin, Q. Zheng, X. Shen, J.R. Pothnis, J. Jia, E.
Zussman, J. Kim, Carbon 59, 406 (2013)
21. T.K.B. Sharmila, J.V. Antony, M.P. Jayakrishnan, P.M.S. Beegum,
E. Thomas, Mater. Des. 90, 66 (2016)
22. Y.T. Lin, T.M. Don, C.J. Wong, F.C. Meng, Y.J. Lin, S.Y. Lee,
C.F. Lee, W.Y. Chiu, Surf. Coat. Technol. (2018). https​://doi.
org/10.1016/j.surfc​oat.2018.01.050
23. Y. Che, Z. Sun, R. Zhan, S. Wang, S. Zhou, J. Huang, Ceram. Int.
44, 18067 (2018)
24. A.K. Singh, A. Parhi, B.P. Panda, S. Mohanty, S.K. Nayak, M.K.
Gupta, J. Mater. Sci.: Mater. Electron. 28, 17655 (2017)
25. A.K. Singh, B.P. Panda, S. Mohanty, S.K. Nayak, M.K. Gupta, J.
Mater. Sci.: Mater. Electron. 28, 8908 (2017)
26. S.M. Suresh Kumar, K. Subramanian, Adv. Polym. Technol. 37,
612 (2016)
27. N. Norhakim, S. Ahmad, C. Chia, N. Huang, Sains Malaysiana
43, 603 (2014)
28. N. Adak, S. Chhetri, N. Murmu, P. Samanta, T. Kuila, Crystals 8,
111 (2018)
29. L.R. Galicia, L.N. Mendez, A.L.M. Hernadez, A.E. Gonzalez,
I.R.G. Esquivel, R.F. Ramirez, C.V. Santos, Int. J. Polym. Sci.
(2013). https​://doi.org/10.1155/2013/49314​7
30. S. Chhetri, N.C. Adak, P. Samanta, N.C. Murmu, T. Kuila, Polym.
Test. 63, 1 (2017)
31. H.J. Salavagione, G. Martínez, G. Ellis, Physics and Applications
of Graphene Experiments (Intech, London, 2013), pp. 169–192
32. W. Li, H. Li, X. Yang, W. Feng, H. Huang, J. Compos. Mater. 51,
1197 (2017)
33. J. Tang, H. Zhou, Y. Liang, X. Shi, X. Yang, J. Zhang, J. Nano-
mater. (2014).https​://doi.org/10.1155/2014/69685​9
34. S.-Y. Lee, M.-H. Chong, M. Park, H.-Y. Kim, S.-J. Park, Carbon
Lett. 15, 67 (2014)
35. R. Aradhana, S. Mohanty, S.K. Nayak, Int. J. Adhes. 84, 238
(2018)
36. Q. Liu, X. Yao, Z. Liu, Adv. Mater. Res. 391, 175 (2012)
37. Y. Sun, L. Chen, J. Lin, P. Cui, M. Li, X. Du, J. Compos. Mater.
51, 1743 (2017)
38. N. Yousefi, X. Lin, X. Shen, J. Jia, J. Kim, ECCM 2014. 1 (2014)
39. N. Yousefi, X.Y. Lin, X. Shen, J.J. Jia, O.J. Dada, J.K. Kim,
ICCM-19, 1 (2013)
40. S. Chhetri, P. Samanta, N. Chandra Murmu, S. Kumar, Srivastava,
T. Kuila, AIMS Mater. Sci. 4, 61 (2016)
41. A. Ravindran, C. Feng, S. Huang, Y. Wang, Z. Zhao, J. Yang,
Polymer (Basel)10, 477 (2018)
42. Y.X. Fu, Z.X. He, D.C. Mo, S.S. Lu, Int. J. Therm. Sci. 86, 276
(2014)
43. G.B. Olowojoba, S. Kopsidas, S. Eslava, E.S. Gutierrez, A.J. Kin-
loch, C. Mattevi, V.G. Rocha, A.C. Taylor, J. Mater. Sci. 52, 7323
(2017)
44. B. Tang, G. Hu, H. Gao, L. Hai, Int. J. Heat Mass Transf. 85, 420
(2015)
45. D. Konios, M.M. Stylianakis, E. Stratakis, E. Kymakis, J. Colloid
Interface Sci. 430, 108 (2014)
46. R. Aradhana, S. Mohanty, S. Kumar, Compos. Sci. Technol. 169,
86 (2019)
47. C. Bora, P. Gogoi, S. Baglari, S.K. Dolui, J. Appl. Polym. Sci.
129, 3432 (2013)